Fundamental atomistic simulation studies of nanoparticle properties

Brian J. Henz1, Takumi Hawa2,3, Michael R. Zachariah2,3

Research Laboratory 2University of Maryland 3National Institute of Standards and Technology
1U.S. Army

Molecular Dynamics Simulation of the Kinetic Reaction of Ni and Al Nanoparticles

Details Gain an understanding of the self-propagating high-temperature synthesis (SHS) reaction of intermetallic compounds Use classical molecular dynamics Highly parallel algorithm Analysis of energetics Size dependence for combustion temperature reaction rate Liquid aluminum and solid nickel Ignition temperature nanoparticles kinetically sintering. Ignition mechanisms
Size dependent combustion temperature
Combustion temperature is highly size dependent and predictable. Small nanoparticles reach a higher temperature because of surface energy affects.

A Scaling Law for Fractal Aggregate Sintering

Details Control both size and structure of nanoparticles in a vapor-phase process Competition between sintering and collision time. Understand the physical mechanism of sintering of nanoparticle fractal aggregate Use MD simulation Develop a simple phenomenological model
Straight chain aggregate

Mechano-Chemical Stability of Gold Nanoparticles Coated with Alkanethiolate SAMs

Details Probe structure and stability of alkanethiolate self-assembled monolayer on gold nanoparticles Use classical molecular dynamics Highly parallel algorithm Compute system properties Pair correlation function Diffusion coefficients Equilibrated SAM coated gold nanoparticle at 300K. Radial pressure Phase behavior and SAM solubility

Size dependent reaction time

Universal relationship that only depends on the chain length Power law model for a sintering of chain aggregate as a function of Df

Diffusion Coefficients Used to compute the mobility of SAMs Diffusion coefficient of head-group gives insight on SAM mobility on surface

Radial Density Computed as intermediate step in radial pressure computation Used as parameter in computation of corrugation factor Defined as difference in core radius from uncoated nanoparticle

Bulk combustion temperature (1600K bulk vs. 2100K for 3nm nanoparticles)

Reaction time for separate nanoparticles is linearly dependent upon number of atoms or nanoparticle volume.

Note that above 500K the ratio is approximately unity, indicating gold and sulfur moving together.

t t Frenkel N 1
4a0 tFrenkel 3

0.68
C=0.107

Ignition mechanisms

Fractal aggregate

Log plot of sulfur diffusivity versus inverse of temperature for fully SAM coated nanoparticle. Slope is related to activation energy for diffusion.

Plot of ratio of sulfur diffusivity to gold diffusivity versus temperature.

C=0.0

Plot of radial density profile for bare, partially coated, and fully coated gold nanoparticle.

Cluster impact of oxide coating and ejection Impulse heating of oxide coated aluminum and nickel nanoparticles

Internal pressure Positive internal pressure is typical Computed for 5nm gold Indicates compressive stress nanoparticle coated with Negative internal pressure is Sulfur only measured for coated nanoparticle Alkanethiol chains with weak Indicates tensile stress Possible, but metaintra-chain potentials stable, because gold is solid at room temperature Alkanethiol chains with strong intra-chain potentials
Power law model for a sintering of fractal aggregate as a function of Df

Coalescence and sintering of uncoated nanoparticles Collision of oxide coated nickel and aluminum nanoparticles

Conclusions Based on reaction time and combustion temperature, the energy release rate is much higher for smaller nanoparticles and is size dependent. High velocity clusters may penetrate oxide shells or cause sufficient damage for failure Kinetic reaction between separate nanoparticles occurs in two stages; first coalescence of liquid aluminum and solid nickel, and secondly sintering of the nanoparticles

t tFrenkel N 1

0.68

Df

Conclusions Sintering of fractal aggregate: MD simulations for chain, fractal, and compact structure aggregate Developed a power law model for any fractal dimensions Excellent agreement with MD results Convenient for an aerosol model

Conclusions Each of the computed results including diffusivisty, pair correlation, internal pressure, and potential energy all indicate that a phase change has occurred at a temperature lower than the bare nanoparticle melting temperature. Intra-chain interactions have a strong affect on nanoparticle stability, more so than chain to surface bond strength. With the observed surface corrugation, an accurate model must consider gold atoms as mobile particles, not fixed.